Synthesis, crystal structures and magnetic properties of a phenoxo-bridged dinuclear Cu(II) complex and a dicyanamide bridged novel molecular rectangle based on it

The phenoxo-bridged dinuclear Cu-II complex [Cu2L2-(NCNCN)(2)] (1) and the dicyanamide-bridged molecular rectangle [Cu4L4{mu(1,5)-(NCNCN)(2)}]center dot(ClO4)(2)(H2O)(2) (2) were synthesized using the tridentate reduced Schiff-base ligand HL {2-[(2-dimethylamino-ethylamino) methyl] phenol}. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 2 was formed through the joining of the phenoxo-bridged dinuclear Cu2O2 cores of 1 via the mu(1,5)-bridging mode of dicyanamide. The structural properties of the Cu2O2 cores in two complexes are significantly different. The geometry of the copper ions is distorted trigonal bipyramid in 1 but is nearly square-pyramidal in 2. These differences have a marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -185.2 and -500.9 cm(-1) for 1 and 2, respectively) differ considerably.

DIFFUSION OF MAGNETIC FIELD AND REMOVAL OF MAGNETIC FLUX FROM CLOUDS VIA TURBULENT RECONNECTION

The diffusion of astrophysical magnetic fields in conducting fluids in the presence of turbulence depends on whether magnetic fields can change their topology via reconnection in highly conducting media. Recent progress in understanding fast magnetic reconnection in the presence of turbulence reassures that the magnetic field behavior in computer simulations and turbulent astrophysical environments is similar, as far as magnetic reconnection is concerned. This makes it meaningful to perform MHD simulations of turbulent flows in order to understand the diffusion of magnetic field in astrophysical environments. Our studies of magnetic field diffusion in turbulent medium reveal interesting new phenomena. First of all, our three-dimensional MHD simulations initiated with anti-correlating magnetic field and gaseous density exhibit at later times a de-correlation of the magnetic field and density, which corresponds well to the observations of the interstellar media. While earlier studies stressed the role of either ambipolar diffusion or time-dependent turbulent fluctuations for de-correlating magnetic field and density, we get the effect of permanent de-correlation with one fluid code, i.e., without invoking ambipolar diffusion. In addition, in the presence of gravity and turbulence, our three-dimensional simulations show the decrease of the magnetic flux-to-mass ratio as the gaseous density at the center of the gravitational potential increases. We observe this effect both in the situations when we start with equilibrium distributions of gas and magnetic field and when we follow the evolution of collapsing dynamically unstable configurations. Thus, the process of turbulent magnetic field removal should be applicable both to quasi-static subcritical molecular clouds and cores and violently collapsing supercritical entities. The increase of the gravitational potential as well as the magnetization of the gas increases the segregation of the mass and magnetic flux in the saturated final state of the simulations, supporting the notion that the reconnection-enabled diffusivity relaxes the magnetic field + gas system in the gravitational field to its minimal energy state. This effect is expected to play an important role in star formation, from its initial stages of concentrating interstellar gas to the final stages of the accretion to the forming protostar. In addition, we benchmark our codes by studying the heat transfer in magnetized compressible fluids and confirm the high rates of turbulent advection of heat obtained in an earlier study.

Characterization of organic matter in sediment cores of the Todos os Santos Bay, Bahia, Brazil, by elemental analysis and (13)C NMR

The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and (13)C Nuclear Magnetic Resonance ((13)C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Auto-regressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the (13)C NMR spectra clearly differentiates sediment samples closer to the Subae estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay. (C) 2011 Elsevier Ltd. All rights reserved.

Magnetic properties of spindle-type iron fine particles obtained from hematite

Spindle-type iron fine particles have been prepared by reduction of silica-coated-hematite particles. Hydrogen reduction of the coated-hematite cores yielded uniform spindle-type iron particles, which were stabilized by surface oxidation. Narrow particle distributions are observed from TEM measurements. X-ray, Mössbauer and magnetization data are in agreement with the presence of nanosized α-Fe particles, having surface layer of spinel structure oxide. Mössbauer spectra show that the oxide surface is superparamagnetic at room temperature. © 2001 Elsevier Science B.V. All rights reserved.

Magnetic flux transport by turbulent reconnection in astrophysical flows

The role of magnetohydrodynamics (MHD) turbulence in astrophysical environments is still highly debated. An important question that permeates this debate is the transport of magnetic flux. This is particularly important, for instance, in the context of star formation. When clouds collapse gravitationally to form stars, there must be some magnetic flux transport. Otherwise, the newborn stars would have magnetic fields several orders of magnitude larger than the observed ones. Also, the magnetic flux that is dragged in the late stages of the formation of a star can remove all the rotational support from the accretion disc that grows around the protostar. The efficiency of the mechanism that is often invoked to allow transport of magnetic fields at different stages of star formation, namely ambipolar diffusion, has recently been put in check. We discuss here an alternative mechanism for magnetic flux transport which is based on turbulent fast magnetic reconnection. We review recent results from three-dimensional MHD numerical simulations that indicate that this mechanism is very efficient in decoupling and transporting magnetic flux from the inner denser regions to the outskirts of collapsing clouds at different stages of star formation. We discuss this mechanism also in the context of dynamo processes and speculate that it can play a role both in solar dynamo and in accretion disc dynamo processes.

THE ROLE OF TURBULENT MAGNETIC RECONNECTION IN THE FORMATION OF ROTATIONALLY SUPPORTED PROTOSTELLAR DISKS

The formation of protostellar disks out of molecular cloud cores is still not fully understood. Under ideal MHD conditions, the removal of angular momentum from the disk progenitor by the typically embedded magnetic field may prevent the formation of a rotationally supported disk during the main protostellar accretion phase of low-mass stars. This has been known as the magnetic braking problem and the most investigated mechanism to alleviate this problem and help remove the excess of magnetic flux during the star formation process, the so-called ambipolar diffusion (AD), has been shown to be not sufficient to weaken the magnetic braking at least at this stage of the disk formation. In this work, motivated by recent progress in the understanding of magnetic reconnection in turbulent environments, we appeal to the diffusion of magnetic field mediated by magnetic reconnection as an alternative mechanism for removing magnetic flux. We investigate numerically this mechanism during the later phases of the protostellar disk formation and show its high efficiency. By means of fully three-dimensional MHD simulations, we show that the diffusivity arising from turbulent magnetic reconnection is able to transport magnetic flux to the outskirts of the disk progenitor at timescales compatible with the collapse, allowing the formation of a rotationally supported disk around the protostar of dimensions similar to 100 AU, with a nearly Keplerian profile in the early accretion phase. Since MHD turbulence is expected to be present in protostellar disks, this is a natural mechanism for removing magnetic flux excess and allowing the formation of these disks. This mechanism dismisses the necessity of postulating a hypothetical increase of the ohmic resistivity as discussed in the literature. Together with our earlier work which showed that magnetic flux removal from molecular cloud cores is very efficient, this work calls for reconsidering the relative role of AD in the processes of star and planet formation.

Fluorescent-magnetic hybrid nanoparticles induce a dose-dependent increase in proinflammatory response in lung cells in vitro correlated with intracellular localization

Iron-platinum nanoparticles embedded in a poly(methacrylic acid) (PMA) polymer shell and fluorescently labeled with the dye ATTO 590 (FePt-PMA-ATTO-2%) are investigated in terms of their intracellular localization in lung cells and potential to induce a proinflammatory response dependent on concentration and incubation time. A gold core coated with the same polymer shell (Au-PMA-ATTO-2%) is also included. Using laser scanning and electron microscopy techniques, it is shown that the FePt-PMA-ATTO-2% particles penetrate all three types of cell investigated but to a higher extent in macrophages and dendritic cells than epithelial cells. In both cell types of the defense system but not in epithelial cells, a particle-dose-dependent increase of the cytokine tumor necrosis factor alpha (TNFalpha) is found. By comparing the different nanoparticles and the mere polymer shell, it is shown that the cores combined with the shells are responsible for the induction of proinflammatory effects and not the shells alone. It is concluded that the uptake behavior and the proinflammatory response upon particle exposure are dependent on the time, cell type, and cell culture.

Novel magnetic iron oxide nanoparticles coated with poly(ethylene imine)-g-poly(ethylene glycol) for potential biomedical application: synthesis, stability, cytotoxicity and MR imaging

Magnetic iron oxide nanoparticles have found application as contrast agents for magnetic resonance imaging (MRI) and as switchable drug delivery vehicles. Their stabilization as colloidal carriers remains a challenge. The potential of poly(ethylene imine)-g-poly(ethylene glycol) (PEGPEI) as stabilizer for iron oxide (γ-Fe₂O₃) nanoparticles was studied in comparison to branched poly(ethylene imine) (PEI). Carrier systems consisting of γ-Fe₂O₃-PEI and γ-Fe₂O₃-PEGPEI were prepared and characterized regarding their physicochemical properties including magnetic resonance relaxometry. Colloidal stability of the formulations was tested in several media and cytotoxic effects in adenocarcinomic epithelial cells were investigated. Synthesized γ-Fe₂O₃ cores showed superparamagnetism and high degree of crystallinity. Diameters of polymer-coated nanoparticles γ-Fe₂O₃-PEI and γ-Fe₂O₃-PEGPEI were found to be 38.7 ± 1.0 nm and 40.4 ± 1.6 nm, respectively. No aggregation tendency was observable for γ-Fe₂O₃-PEGPEI over 12 h even in high ionic strength media. Furthermore, IC₅₀ values were significantly increased by more than 10-fold when compared to γ-Fe₂O₃-PEI. Formulations exhibited r₂ relaxivities of high numerical value, namely around 160 mM⁻¹ s⁻¹. In summary, novel carrier systems composed of γ-Fe₂O₃-PEGPEI meet key quality requirements rendering them promising for biomedical applications, e.g. as MRI contrast agents.

Iron(III)-Pivalate-Based Complexes with Tetranuclear {Fe-4(mu(3)-O)(2)}(8+) Cores and N-Donor Ligands: Formation of Cluster and Polymeric Architectures

Different synthetic routes have been used for the preparation of a new tetranuclear [Fe4O2(O2CCMe3)(8)(bpm)] cluster (1) and a one-dimensional coordination polymer [Fe4O2-(O2CCMe3)(8)(hmta)](n) (2) (bpm = 2,2'-bipyrimidine and hmta = hexamethylenetetramine). For cluster 1, two structural isomers, 1a and 1b center dot 3MeCN, have been found. X-ray crystallographic analysis showed that all complexes consist of a central {Fe-4(mu(3)-O)(2)}(8+) core. In 1a, metal ions in the core are additionally linked by six bridging pivalates as two other pivalates and a bpm ligand are chelated to Fe-III ions, whereas in cluster 1b, metal ions in the {Fe-4(mu(3)-O)(2)}(8+) core are linked by seven bridging pivalates and only one carboxylate as well as bpm are chelated to the iron centers. In coordination polymer 2, [Fe4O2(O2CCMe3)(8)] clusters are bridged by hmta ligands to form zigzag chains. Magnetic measurements have been carried out to characterize these complexes and revealed antiferromagnetic interactions between Fe-III ions with best-fit parameters of J(wb) = -72.2 (1a) and -88.7 cm(-1) (1b) for wing...body interactions.

A centrifugal ice microtome for measurements of atmospheric CO₂ on air trapped in polar ice cores

For atmospheric CO2 reconstructions using ice cores, the technique to release the trapped air from the ice samples is essential for the precision and accuracy of the measurements. We present here a new dry extraction technique in combination with a new gas analytical system that together show significant improvements with respect to current systems. Ice samples (3–15 g) are pulverised using a novel centrifugal ice microtome (CIM) by shaving the ice in a cooled vacuum chamber (−27 °C) in which no friction occurs due to the use of magnetic bearings. Both, the shaving principle of the CIM and the use of magnetic bearings have not been applied so far in this field. Shaving the ice samples produces finer ice powder and releases a minimum of 90% of the trapped air compared to 50%–70% when needle crushing is employed. In addition, the friction-free motion with an optimized design to reduce contaminations of the inner surfaces of the device result in a reduced system offset of about 2.0 ppmv compared to 4.9 ppmv. The gas analytical part shows a higher precision than the corresponding part of our previous system by a factor of two, and all processes except the loading and cleaning of the CIM now run automatically. Compared to our previous system, the complete system shows a 3 times better measurement reproducibility of about 1.1 ppmv (1 σ) which is similar to the best reproducibility of other systems applied in this field. With this high reproducibility, no replicate measurements are required anymore for most future measurement campaigns resulting in a possible output of 12–20 measurements per day compared to a maximum of 6 with other systems.

Geochemical and physical sediment properties of sediment cores from the Portuguese shelf

Marine sediments from the Portuguese shelf are influenced by environmental changes in the surrounding continental and marine environment. These are largely controlled by the North Atlantic Oscillation, but additional impacts may arise from episodic tsunamis. In order to investigate these influences, a high resolution multi-proxy study has been carried out on a 5.4 m long gravity core and five box cores from the Tagus prodelta on the western Portuguese margin, incorporating geochemical (Corg/Ntotal ratios, d13Corg, d15N, d18O, Corg and CaCO3 content) and physical sediment properties (magnetic susceptibility, grain-size). Subsurface data of the five box cores indicate no major effect of early postdepositional alteration. Surface data show a higher fraction of terrigenous organic material close to the river mouth and in the southern prodelta. Gravity core GeoB 8903 covers the last 3.2 kyrs with a temporal resolution of at least 0.1 cm/yr. Very high sedimentation rates between 69 and 140 cm core depth indicate a possible disturbance of the record by the AD1755 tsunami, although no evidence for a disturbance is observed in the data. Sea surface temperature and salinity on the prodelta, the local budget of marine NO3- as well as the provenance of organic matter remained virtually constant during the past 3.2 kyrs. A positive correlation between magnetic susceptibility (MS) and North Atlantic Oscillation (NAO) is evident for the past 250 years, coinciding with a negative correlation between mean grain-size and NAO. This is assigned to a constant riverine supply of fine material with high MS, which is diluted by the riverine input of a coarser, low-MS component during NAO negative, high-precipitation phases. End-member modelling of the lithic grain-size spectrum supports this, revealing a third, coarse lithic component. The high abundance of this coarse end-member prior to 2 kyr BP is interpreted as the result of stronger bottom currents, concentrating the coarse sediment fraction by winnowing. As continental climate was more arid prior to 2 kyr BP (Subboreal), the coarse end-member may also consist of dust from local sources. A decrease in grain-size and CaCO3 content after 2 kyr BP is interpreted as a result of decreasing wind strength. The onset of a fining trend and a further decrease in CaCO3 around AD900 occurs simultaneous to climatic variations, reconstructed from eastern North Atlantic records. A strong increase in MS between AD1400 and AD1500 indicates higher lithic terrigenous input, caused by deforestation in the hinterland.